CN112538047A - Organic compound with symmetrical hetero-substituted azaspirobifluorene structure and application thereof - Google Patents
Organic compound with symmetrical hetero-substituted azaspirobifluorene structure and application thereof Download PDFInfo
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- CN112538047A CN112538047A CN201910894427.3A CN201910894427A CN112538047A CN 112538047 A CN112538047 A CN 112538047A CN 201910894427 A CN201910894427 A CN 201910894427A CN 112538047 A CN112538047 A CN 112538047A
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- substituted
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- unsubstituted
- compound
- organic compound
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 230000005525 hole transport Effects 0.000 claims abstract description 31
- 238000002347 injection Methods 0.000 claims abstract description 28
- 239000007924 injection Substances 0.000 claims abstract description 28
- 230000000903 blocking effect Effects 0.000 claims abstract description 17
- 239000011368 organic material Substances 0.000 claims description 27
- -1 quaterphenyl Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000007740 vapor deposition Methods 0.000 abstract description 4
- 125000005264 aryl amine group Chemical group 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 102
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 42
- 239000000543 intermediate Substances 0.000 description 31
- 238000004128 high performance liquid chromatography Methods 0.000 description 26
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 15
- 238000002061 vacuum sublimation Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical class C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RNIUHIHTGPHJEN-AWEZNQCLSA-N 2-[(3S)-1-[2-(3,4-dichlorophenyl)acetyl]piperidin-3-yl]oxy-6-(trifluoromethyl)pyridine-4-carbonitrile Chemical compound ClC=1C=C(C=CC=1Cl)CC(=O)N1C[C@H](CCC1)OC=1C=C(C#N)C=C(N=1)C(F)(F)F RNIUHIHTGPHJEN-AWEZNQCLSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 125000005266 diarylamine group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- UOMXLEWVJZEVGP-UHFFFAOYSA-N 4-tert-butyl-n-phenylaniline Chemical compound C1=CC(C(C)(C)C)=CC=C1NC1=CC=CC=C1 UOMXLEWVJZEVGP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HKRVHTFXSUGWIV-UHFFFAOYSA-N 1,1'-spirobi[fluorene]-2'-amine Chemical class C12=CC3=CC=CC=C3C1=CC=CC12C2=CC3=CC=CC=C3C2=CC=C1N HKRVHTFXSUGWIV-UHFFFAOYSA-N 0.000 description 1
- WSHZWUXRWQVZQP-UHFFFAOYSA-N 1-bromo-2-(4-chlorophenyl)benzene Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1Br WSHZWUXRWQVZQP-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical group N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- YFCSASDLEBELEU-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene-11,12,15,16,17,18-hexacarbonitrile Chemical group N#CC1=C(C#N)C(C#N)=C2C3=C(C#N)C(C#N)=NN=C3C3=NN=NN=C3C2=C1C#N YFCSASDLEBELEU-UHFFFAOYSA-N 0.000 description 1
- LXOCTSJQHHCASE-UHFFFAOYSA-N 3-phenyl-n-(3-phenylphenyl)aniline Chemical compound C=1C=CC(C=2C=CC=CC=2)=CC=1NC(C=1)=CC=CC=1C1=CC=CC=C1 LXOCTSJQHHCASE-UHFFFAOYSA-N 0.000 description 1
- JAUCIDPGGHZXRP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)aniline Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1NC(C=C1)=CC=C1C1=CC=CC=C1 JAUCIDPGGHZXRP-UHFFFAOYSA-N 0.000 description 1
- OBARUOOPPWHZRQ-UHFFFAOYSA-N 9,9-dimethyl-n-(2-phenylphenyl)fluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1NC1=CC=CC=C1C1=CC=CC=C1 OBARUOOPPWHZRQ-UHFFFAOYSA-N 0.000 description 1
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- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical class C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- GCKUQDNLPXLMHM-UHFFFAOYSA-N BrC=1C(C2=CC3=NC=CC=C3C2=CC1)=O Chemical compound BrC=1C(C2=CC3=NC=CC=C3C2=CC1)=O GCKUQDNLPXLMHM-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical class C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- QKBTTXJHJNXCOQ-UHFFFAOYSA-N dibenzofuran-4-amine Chemical compound O1C2=CC=CC=C2C2=C1C(N)=CC=C2 QKBTTXJHJNXCOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 150000002219 fluoranthenes Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
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- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YGNUPJXMDOFFDO-UHFFFAOYSA-N n,4-diphenylaniline Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 YGNUPJXMDOFFDO-UHFFFAOYSA-N 0.000 description 1
- KDADHQHDRSAQDY-UHFFFAOYSA-N n-(4-phenylphenyl)naphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1NC(C=C1)=CC=C1C1=CC=CC=C1 KDADHQHDRSAQDY-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical class C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000002964 pentacenes Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 238000001931 thermography Methods 0.000 description 1
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- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
Abstract
The invention provides an organic compound with a symmetrical hetero-substituted azaspirobifluorene structure and application thereof. The organic compound with the symmetrical iso-substituted azaspirobifluorene structure has a structure shown in a formula (1). The compound takes azaspirobifluorene as a main body, and different arylamine groups are introduced at symmetrical positions, so that the glass transition temperature and the thermal stability of the compound are improved. Meanwhile, the compound has higher carrier transport capability. The combination ofThe compound is suitable for fluorescent or phosphorescent OLEDs, in particular phosphorescent OLED devices, can be used as a host material of a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer, and is beneficial to improving the efficiency and the service life of the device. In addition, the compound is relatively simple to synthesize and purify, is not easy to crystallize during vapor deposition, and has good film forming property.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent elements, in particular to an organic compound with a symmetrical hetero-substituted azaspirobifluorene structure and application thereof.
Background
An organic electroluminescent element (OLED) generally has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Here, the organic material layer generally includes functional layers such as a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The performance of the OLED device is closely related to the physical and chemical properties of the organic materials, and the functional materials have strong selectivity and need to be reasonably matched to achieve the optimal device performance. At present, the development of organic compounds with different functions is still the focus of research, and the development of organic compounds with low cost and simple synthesis steps has important significance for OLED industrialization.
The hole transport layer is the thickest organic film layer in the OLED device, so the film forming property and the thermal stability of the hole transport material have non-negligible influence on the device performance. In the prior art, the hole transport materials widely used are generally triarylamine derivatives, generally derived from diarylamino-substituted triphenylamines (TPA type), diarylamino-substituted biphenyl derivatives (TAD type) or combinations of these base compounds.
Spirobifluorene derivatives, which are a member of polycyclic aromatic hydrocarbons, have high thermal stability, are capable of sublimation without decomposition and residue, and are particularly useful as charge transport materials in OLED devices. CN108137480A discloses a spirobifluorene 2, 4' -disubstituted compound which exhibits low voltage and high efficiency when used as a hole transport layer and a hole regulating layer (i.e., an electron blocking layer) of an OLED device. CN105720203A discloses spirobifluorene 2,2 '-disubstituted, 2, 3' -disubstituted, 2 ', 6' -trisubstituted and 2,3 ', 6' -trisubstituted compounds, which exhibit high efficiency and long lifetime when used as hole transport layers in OLED devices. However, in order to meet the requirement of mass production of OLEDs, the carrier transport property and thermal stability of the compounds still need to be further improved.
Disclosure of Invention
The invention mainly aims to provide an organic compound with a symmetrical hetero-substituted azaspirobifluorene structure, so as to solve the problem that the spirobifluorene derivative in the prior art is insufficient in carrier transport property and thermal stability.
In order to achieve the above object, according to one aspect of the present invention, there is provided an organic compound having a symmetrical iso-substituted azaspirobifluorene structure, characterized by having a structure represented by formula (1):
in the formula (1), Z1、Z2、Z3、Z4Of which only one is a nitrogen atom and the remainder are CR1；Ar1、Ar2、Ar3、Ar4Each independently represents a substituted or unsubstituted aryl or heterocyclic aryl group, and Ar1And Ar2Optionally by E1Are linked to each other to form a ring, Ar3And Ar4Optionally by E2Are connected with each other to form a ring; e1And E2Each independently represents a single bond, CR2R3、NR4-O-or-S-; ar (Ar)1(Ar2)N-(L1)m-and- (L)2)n-NAr3(Ar4) Different, the substitution positions of the two are symmetrical by taking the spiro carbon atom as the center; l is1And L2Each independently represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring-forming carbon atoms; m and n each independently represent an integer of 0 to 3, and when m > 1, m L1Are the same or different from each other, when n > 1, n L2Are the same or different from each other; r1、R2、R3、R4Each independently represents hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted alkyl groupAn unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group.
According to another aspect of the present invention there is provided the use of an organic compound having a symmetrical iso-substituted azaspirobifluorene structure as described above in an OLED device.
According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a cathode, an anode and one or more organic material layers disposed between the cathode and the anode, wherein at least one of the organic material layers comprises the organic compound
The organic compound provided by the invention has a symmetrical hetero-substituted azaspirobifluorene structure, takes azaspirobifluorene as a main body, and introduces different arylamine groups at symmetrical positions, so that the glass transition temperature and the thermal stability of the compound are improved, and meanwhile, the compound has higher carrier transport capability. The compound is suitable for fluorescent or phosphorescent OLEDs, particularly phosphorescent OLED devices, can be used as a host material of a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer, and is beneficial to improving the efficiency and the service life of the device. In addition, the compound is relatively simple to synthesize and purify, is not easy to crystallize during vapor deposition, and has good film forming property.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the spirobifluorene derivatives in the prior art have insufficient performance in terms of carrier transport property and thermal stability, and it is difficult to meet the requirement of mass production of OLEDs.
In order to solve the above problems, the present invention provides an organic compound having a symmetrical iso-substituted azaspirobifluorene structure, which has a structure represented by formula (1):
in the formula (1), Z1、Z2、Z3、Z4Of which only one is a nitrogen atom and the remainder are CR1；Ar1、Ar2、Ar3、Ar4Each independently represents a substituted or unsubstituted aryl or heterocyclic aryl group, and Ar1And Ar2Optionally by E1Are linked to each other to form a ring, Ar3And Ar4Optionally by E2Are connected with each other to form a ring; e1And E2Each independently represents a single bond, CR2R3、NR4-O-or-S-; ar (Ar)1(Ar2)N-(L1)m-and- (L)2)n-NAr3(Ar4) Different, the substitution positions of the two are symmetrical by taking the spiro carbon atom as the center; l is1And L2Each independently represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring-forming carbon atoms; m and n each independently represent an integer of 0 to 3, and when m > 1, m L1Are the same or different from each other, when n > 1, n L2Are the same or different from each other; r1、R2、R3、R4Each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group.
The organic compound provided by the invention has a symmetrical hetero-substituted azaspirobifluorene structure, takes azaspirobifluorene as a main body, and introduces different arylamine groups at symmetrical positions, so that the glass transition temperature and the thermal stability of the compound are improved, and meanwhile, the compound has higher carrier transport capability. The compound is suitable for fluorescent or phosphorescent OLEDs, particularly phosphorescent OLED devices, can be used as a host material of a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer, and is beneficial to improving the efficiency and the service life of the device. In addition, the compound is relatively simple to synthesize and purify, is not easy to crystallize during vapor deposition, and has good film forming property.
In order to further improve the carrier transporting property and thermal stability of the above organic compound, in a preferred embodiment, in formula (1), Ar is1、Ar2、Ar3、Ar4Each independently represents a substituted or unsubstituted phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl or spirobifluorenyl group, or a substituted or unsubstituted dibenzothienyl, dibenzofuranyl or carbazolyl group. More preferably, in the formula (1), L1And L2Are all single bonds, i.e. the N atom is directly connected with the benzene ring of the azaspirobifluorene. Further preferably, m and n each independently represent 0 or 1.
Preferably, in the formula (1), R1To R4Each independently represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, phenyl, 1-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, methoxy. More preferably, R1To R4Each independently represents hydrogen or phenyl.
As a preferable embodiment of the present invention, the organic compound is represented by any one of the following formulas (2) to (5):
and in formulae (2) to (5), Z1、Z2、Z3、Z4、Ar1、Ar2、Ar3And Ar4Have the same definitions as above.
Exemplarily, formula (1) is represented by any one of the following formulae (6) to (21):
and in formulae (6) to (21), Ar1、Ar2、Ar3And Ar4Have the same definitions as above.
In a preferred embodiment, Ar1、Ar2、Ar3And Ar4Each independently selected from the following structures:
wherein R is5、R6And R7Each independently is hydrogen, deuterium, a halogen group, a cyano group, a silyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted boron atom, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Ar of the above structure1To Ar4The carrier transport capacity of the organic compound with an azaspirobifluorene structure can be further improved. Particularly preferably, based on formula (1), some preferred examples of the organic compounds according to the invention are listed below:
the above organic compounds of the present invention can be prepared by synthetic methods known to those of ordinary skill in the art such as Buchwald-Hartwig coupling (C-N coupling). Different diarylamino groups are introduced step by the sequential reaction of dihalogenated azaspirobifluorene and different diarylamines to obtain the target compound.
Illustratively, a suitable preparation method is described below by way of example for the synthesis of a compound of formula (1), wherein L is a single bond and R is1To R4Is H.
Under the action of an N-butyllithium reagent, dihalobiphenyl and the intermediate A are added to obtain an intermediate B, the intermediate B is hydrolyzed and cyclized to generate an intermediate C, and the intermediate C and two diarylamines are distributed to perform C-N coupling reaction to obtain the target compound.
In view of the excellent properties of the above organic compounds of the present invention, the present invention also provides specific applications of the above organic compounds in OLED devices. The method comprises the following specific steps:
according to an aspect of the present invention, there is also provided the use of the above organic compound having a symmetrically iso-substituted azaspirobifluorene structure in an OLED device. As mentioned above, the organic compound has a high glass transition temperature, good thermal stability, and good carrier transport property, so that it is useful for improving the efficiency and prolonging the lifetime of the device when applied to the OLED device.
According to another aspect of the present invention, there is provided an organic electroluminescent element comprising a cathode, an anode and one or more organic material layers disposed between the cathode and the anode, at least one of the organic material layers comprising the above organic compound. Specifically, the organic material layer of the OLED device may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the OLED device may include a plurality of organic material layers such as a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer in a direction from the anode to the cathode. The anode is typically disposed substantially above the transparent.
In a typical embodiment, at least one of the organic material layers is a hole injection layer, and at least one of the hole injection layers contains the organic compound described above.
In another exemplary embodiment, the organic material layer is a multilayer, at least two layers of which are hole transport layers, and at least one of the hole transport layers contains the above-described organic compound.
In another exemplary embodiment, the organic material layer is a plurality of layers, at least one of which is a hole transport layer and at least one of which is a hole injection layer, and both the hole transport layer and the hole injection layer contain the above-described organic compound. More preferably, the hole injection layer is a mixture of doped P-dopant materials and the hole transport layer is a single layer of compound material.
In another exemplary embodiment, the organic material layer is a plurality of layers, at least one of which is an electron blocking layer, and the electron blocking layer includes the above-described organic compound.
The preparation process of the organic electroluminescent element can adopt the following modes:
method one, applying one or more layers by means of a sublimation method, wherein the vacuum in the vacuum sublimation apparatus should generally be below 10 degrees f-5Mbar, preferably below 10-6The material is deposited at an initial pressure of millibar, which may further preferably be less than 10 for device lifetime-7Initial pressure in millibar.
Method two, applying one or more layers by the OVPD (organic vapor deposition) method or sublimation with the aid of a carrier gas, where 10-5The material is applied at a pressure of mbar to 1 bar. A specific example of such a method is the OVJP (organic vapour jet printing) method, where the material is applied directly through a nozzle.
Method three, the layer or layers are produced by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (photo induced thermal imaging, thermal transfer) or inkjet printing. When the method is adopted, some soluble organic compounds with azaspirobifluorene structures are necessarily adopted, and high solubility can be realized through proper substitution.
The cathode of the OLED device is preferably ofThe low work function metal (alkaline earth metal, alkali metal, main group metal or lanthanoid), metal alloy (alloy of alkali metal or alkaline earth metal and silver) may be a single layer structure or a multilayer structure. In the case of a multilayer structure, in addition to the metals having a low work function described above, other metals having a relatively high work function, such as Ag or Al, can also be used, usually combinations of metals, such as Ca/Ag, Mg/Ag or Ag/Ag. It may also be preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. The intermediate layer can be an alkali metal fluoride or an alkaline earth metal fluoride, or a corresponding oxide or carbonate (e.g., LiF, LiQ, BaF)2、MgO、NaF、CsF、Cs2CO3Etc.).
The anode of the OLED device preferably comprises a metal material with a high work function, such as Ag, Pt or Au. On the other hand, metal/metal oxide materials (e.g., Al/Ni/NiO, Al/PtO) may also be preferred2. Particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO).
The hole injection layer of the OLED device facilitates the reception of holes from the anode at low voltages and preferably the Highest Occupied Molecular Orbital (HOMO) of the hole injection material should be guaranteed between the work function of the anode material and the HOMO of the surrounding organic material layer, including but not limited to metalloporphyrins, oligothiophenes, anthraquinones, arylamine-based, hexacyano-Hexaazatriphenylene (HATCN), quinacridone-and perylene-based organic materials, polyaniline-and polythiophene-based conductive polymers, and the like.
The hole transport layer of the OLED device may receive holes from the anode or the hole injection layer and transport them to the light emitting layer, and the hole transport material needs to have high hole mobility, including arylamine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated units, and the like, but is not limited thereto.
The electron blocking layer of the OLED device may block further transport of electrons in the light emitting layer to the anode to improve light emitting efficiency, and the electron blocking material needs to have a suitably high LUMO energy level, including, but not limited to, amine derivatives, fused aromatic amine derivatives, hexaazatriphenylene derivatives, fluorenamine derivatives, spirobifluorenamine derivatives, benzindenofluorenamine derivatives, and the like.
The light-emitting layer of the OLED device may receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and cause the combined hole and electron radiation to emit light. The host material of the light-emitting layer includes, but is not limited to, a fused aromatic ring derivative such as an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, and a fluoranthene compound, and a heteroaromatic ring derivative such as a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, and a pyrimidine derivative.
The guest doping material of the light emitting layer of the OLED device includes aromatic amine derivatives, styramine compounds, fluoranthene compounds, metal complexes, and the like, but is not limited thereto.
The electron transport layer of the OLED device can receive electrons from the cathode and transport the electrons to the light emitting layer, and the electron transport material needs to have high electron mobility, including derivatives such as oxazole, oxadiazole, triazole, imidazole, fluorenone, anthrone, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but is not limited thereto.
The OLED device can be of a top-emitting type, a bottom-emitting type or a bidirectional-emitting type according to different light emitting directions.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation examples
1. Synthesis of intermediate C
(1) Synthesis of intermediate C1
The synthesis steps are as follows:
fully drying an experimental device, adding 122g of 2-bromo-4 '-chloro-1, 1' -biphenyl (456mmo1) and 1300mL of dried tetrahydrofuran into a 2L four-neck flask under the protection of nitrogen, stirring to dissolve, cooling to below-78 ℃ by using liquid nitrogen, and slowly dropwise adding 182.5mL of 2.5M (456mmol) n-BuLi n-hexane solution; stirring for 1h at-78 ℃ after the dropwise addition is finished, then adding 113g (434.5mmo1) of 2-bromo-8-azafluorenone solid in batches at the temperature, preserving the temperature for 1h at-78 ℃ after the addition is finished, naturally heating to room temperature, and stirring for 8 h. After the reaction is finished, 4M hydrochloric acid solution is dripped to quench the reaction, ethyl acetate is used for extraction, the organic phase is washed by saturated saline solution, and the solvent is removed by spin drying to obtain intermediate alcohol B1. Without any purification, a 2L dry three-necked flask was charged with acetic acid (800 mL) and 36% hydrochloric acid (10 g), and the reaction was terminated by heating and refluxing for 3 hours. After cooling to room temperature, filtration, washing twice with water, drying and recrystallization from toluene and ethanol gave 101g of off-white solid product C1 in 54% yield and 99.6% HPLC purity. MS [ M + H ]]+＝430.16。
(2) Intermediate C2-C4
Referring to the preparation method of intermediate C1, intermediates C2-C4 were synthesized by using different starting materials. As shown in table 1 below.
TABLE 1
2. Synthesis of intermediate D
And respectively reacting the intermediate C with diarylamine to obtain the target compound.
(1) Synthesis of intermediate D1
The synthesis steps are as follows:
the experimental set-up was thoroughly dried and to a 500mL four-necked flask were added under nitrogen gas C119.4 g (45mmol) and 10.1g (45mmol) of 4-tert-butyl-N-phenylaniline, 250mL of dried and degassed toluene as solvent, 6.5g (67.5mmol) of sodium tert-butoxide, 0.4g (0.45mmol) of Pd2(dba)3The catalyst and 0.8g of 1,1' -bis (diphenylphosphino) ferrocene (dppf) are heated to 100 ℃ and 105 ℃ for reaction for 16 hours. After the reaction was complete, it was cooled to room temperature, diluted with toluene, filtered over silica gel, and the filtrate was vacuum distilled to remove the solvent to give a crude product, which was then dissolved in xylene for decolorization and recrystallized to give 22.8g of intermediate D1 in 77% yield and 99.3% purity by HPLC. Elemental analysis (C)40H25ClN2): found value C: 84.35, H: 4.46, Cl: 6.17, N: 5.02. MS [ M + H ]]+＝569.23。
(2) Synthesis of intermediates D2-D8
Referring to the preparation of intermediate D1, intermediates D2-D8 were synthesized by reacting the various intermediates C1-C4 with 4-tert-butyl-N-phenylaniline or N-phenylbiphenyl-4-amine. As shown in table 2 below.
TABLE 2
(3) Synthesis of target Compound
The target compound can be synthesized by the following process:
preparation example 1-1:
the synthesis steps are as follows:
the experimental apparatus was thoroughly dried, and D122.8g (40mmol) and 9.6g (44mmol) of N-phenylnaphthalene-1-amine were introduced into a 500mL four-necked flask under nitrogen, 300mL of dried and degassed toluene was further added, and 5.8g (60mmol) of sodium tert-butoxide and 0.75g (0.8mmol) of Pd were added2(dba)3And heating the catalyst to 80 ℃, slowly dropwise adding 2mL of tri-tert-butylphosphine/toluene solution with the mass concentration of 10%, heating to 100-105 ℃ after dropwise adding, and reacting for 6 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with 200-300 silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, recrystallizing the crude product with a mixed solvent of toluene and n-hexane to obtain 23.1g of the target compound 1-1, wherein the yield is 71%, the HPLC purity is 99.71%, and finally purifying for 2 times through vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝758.42。
Preparation examples 1 to 2:
compounds 1-4 were prepared using the same synthetic procedure as compound 1-1, except that N-phenyl- [1, 1' -biphenyl was used]-3-amine instead of N-phenylnaphthalen-1-amine. The yield is 67%, the HPLC purity is 99.56%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝784.42。
Preparation examples 1 to 3:
compounds 1-46 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D5 was used instead of D1, and N-phenyl- [ dibenzofuran-4-amine was used instead of N-phenylnaphthalen-1-amine. The yield is 67%, the HPLC purity is 99.49%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝818.37。
Preparation examples 1 to 4:
compound 2-2 was prepared using the same synthetic procedure as Compound 1-1, except that intermediate D2 was used instead of D1, and N-phenylnaphthalene-2-amine was used instead of N-phenylnaphthalene-1-amine. The yield is 69%, the HPLC purity is 99.52%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝758.41。
Preparation examples 1 to 5:
compounds 2-34 were prepared using the same synthetic procedure as for compound 1-1, except that intermediate D2 was used in place of D1, N- [1, 1' -biphenyl]-2-yl-9, 9-dimethyl-9H-fluoren-2-amine instead of N-phenylnaphthalen-1-amine. The yield is 67%, the HPLC purity is 99.56%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝901.25。
Preparation examples 1 to 6:
compounds 2-57 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D6 was used instead of D1 and bis (1, 1' biphenyl) -4-yl-amine was used instead of N-phenylnaphthalen-1-amine. The yield is 72%, the HPLC purity is 99.62%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝880.43。
Preparation examples 1 to 7:
compounds 3-13 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D3 was used in place of D1, N- [1, 1' biphenyl]-4-yl-1-naphthylamine instead of N-phenylnaphthalen-1-amine. The yield is 66%, the HPLC purity is 99.51%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝834.45。
Preparation examples 1 to 8:
compounds 3-22 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D3 was used instead of D1, N- [1, 1' biphenyl-4-yl]-9, 9-dimethyl-9H-fluoren-2-amine instead of N-phenylnaphthalen-1-amine. The yield is 74%, the HPLC purity is 99.51%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝900.54。
Preparation examples 1 to 9:
compounds 3-77 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D7 was used instead of D1 and bis- (9, 9-dimethylfluorene) amine was used instead of N-phenylnaphthalen-1-amine. The yield is 64%, the HPLC purity is 99.56%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝960.49。
Preparation examples 1 to 10:
preparation of Compound 1-1 Using the same synthetic routeObject 4-8, except that intermediate D4 was used instead of D1, N-phenyl-3-dibenzofuran-2-amine instead of N-phenylnaphthalen-1-amine. The yield is 66%, the HPLC purity is 99.63%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝798.39。
Preparation examples 1 to 11:
compounds 4-68 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D8 was used in place of D1 and bis- (3-biphenylyl) amine was used in place of N-phenylnaphthalene-1-amine. The yield is 73%, the HPLC purity is 99.67%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝880.44。
Preparation examples 1 to 12:
compounds 4-80 were prepared using the same synthetic procedure as compound 1-1, except that intermediate D8 was used instead of D1 and phenothiazine was used instead of N-phenylnaphthalen-1-amine. The yield is 65%, the HPLC purity is 99.48%, and finally the purification is carried out for 2 times by vacuum sublimation, and the HPLC purity is 99.99%; MS [ M + H ]]+＝758.37。
Performance characterization
3. Physical properties of the compound
The thermal properties, HOMO level and LUMO level of the compound of formula (1) of the present invention were examined using some of the compounds as examples. The test subjects and the results thereof are shown in table 3 below.
TABLE 3
Wherein the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC25 differential scanning calorimeter of TA company in USA), and the heating rate is 10 ℃/min; the thermal weight loss temperature Td is the temperature at which 1% of weight is lost in a nitrogen atmosphere, and is measured on a TGA55 thermogravimetric analyzer of the company TA of America, and the nitrogen flow is 20 mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level are measured by cyclic voltammetry.
As can be seen from the data in Table 3, the compound of the present invention has a higher glass transition temperature, and can ensure the thermal stability of the compound, thereby preventing the amorphous thin film of the compound from being transformed into a crystalline thin film, and improving the lifetime of the OLED device containing the organic compound of the present invention. Meanwhile, the compound has different HOMO and LOMO energy levels, and can be applied to different functional layers in OLED devices.
OLED device applications
The above organic compounds of the present invention are particularly useful for a Hole Injection Layer (HIL), a Hole Transport Layer (HTL) or an Electron Blocking Layer (EBL) in an OLED device.
The effect of the organic compounds of the present invention as materials for different functional layers in OLED devices is detailed below by means of specific examples.
The structural formula of the organic material used is as follows:
the above organic materials are all known compounds on the market and are purchased from the market.
Example A1
A glass substrate (Corning glass 50mm 0.7mm) plated with an ITO (indium tin oxide) anode with the thickness of 130nm is ultrasonically washed for 10min and 2 times respectively by pure water, then dried, treated by plasma for 60s, and then conveyed to a vacuum deposition chamber to deposit each layer of organic material.
The hole injection material HAT-CN was evacuated to a thickness of 5nm (about 10nm)-7Torr) thermal deposition on a transparent ITO electrode, thereby forming a hole injection layer; depositing compound 1-1 with the thickness of 110nm on the hole injection layer in vacuum to form a hole transport layer; depositing HT2 with the thickness of 20nm on the hole transport layer in vacuum to form an electron blocking layer; as a light emitting layer, a host EB and 4% of a guest dopant BD were vacuum-deposited to a thickness of 25 nm; an electron transport layer was formed using an ET compound doped with 5% LiQ (8-hydroxyquinoline lithium) to a thickness of 25 nm; finally, lithium fluoride (an electron injection layer) with the thickness of 1nm and aluminum with the thickness of 150nm are deposited in sequence to form a cathode; after evaporation the device was transferred from the deposition chamber into a glove box and then encapsulated with a UV curable epoxy and a glass cover plate containing a moisture absorber.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 1-1(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
In the above manufacturing steps, the deposition rates of the organic material, lithium fluoride and aluminum were maintained at 0.1nm/s, 0.05nm/s and 0.2nm/s, respectively.
Example A2
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compound 1-4 was used in place of compound 1-1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 1-4(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A3
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compound 2-2 was used in place of compound 1-1 in example a 1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 2-2(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A4
An experiment was performed in the same manner as in example 1 except that: as the hole transporting layer, compounds 2 to 34 were used in place of compound 1 to 1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 2-34(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A5
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compounds 3 to 13 were used in place of compound 1 to 1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 3-13(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A6
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compounds 3 to 77 were used in place of compound 1 to 1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 3-77(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A7
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compound 4-8 was used in place of compound 1-1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 4-8(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example A8
An experiment was performed in the same manner as in example a1, except that: as the hole transporting layer, compounds 4 to 68 were used in place of compound 1 to 1 in example A1.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 4-68(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Comparative example A
An experiment was performed in the same manner as in example a1, except that: as the hole transport layer, HT1 was used instead of compound 1-1 in example a 1.
The device structure is represented as: ITO (130nm)/HAT-CN (5nm)/HT1(110nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Compared with the comparative example A, the device manufacturing process in the device examples A1-A8 is completely the same, the same substrate and electrode material are adopted, the film thickness of the electrode material is kept consistent, and the hole transport material HT1 in the device is replaced.
The devices obtained in examples A1-A8 and comparative example A were placed at 10mA/cm2The performance tests were performed at current densities and the results are shown in table 4.
TABLE 4
Wherein the emission color is represented by CIEx,yJudging and defining chromaticity coordinates; the driving voltage is 1cd/m in luminance2Voltage of (d); the current efficiency refers to the luminous brightness under unit current density; luminous efficiency refers to the luminous flux produced by consuming a unit of electric power; external Quantum Efficiency (EQE) refers to the ratio of the number of photons exiting the surface of the component in the observation direction to the number of injected electrons. LT97@1000nits refers to the lifetime experienced by the OLED device when it was continuously lit at an initial luminance of 1000nits, with the luminance dropping to 97% of the initial luminance.
As shown in the above table, the compounds used in examples a1-A8, which were used as hole transport layers in organic light emitting devices, had excellent hole transport ability and exhibited low voltage and high efficiency characteristics, as compared to the benzidine-type material in comparative example a. In addition, the lifetime of the device is also improved.
To further verify the performance advantages of the present invention, an OLED device having the following structure was fabricated in the manner described above in example 1.
Example B1
The device structure is represented as: ITO (130 nm)/compound 1-46: HT3 (2%) (20 nm)/compound 1-46(105nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example B2
The device structure is represented as: ITO (130 nm)/compound 2-34 HT3 (2%) (20 nm)/compound 2-34(105nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example B3
The device structure is represented as: ITO (130 nm)/compound 3-77: HT3 (2%) (20 nm)/compound 3-77(105nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example B4
The device structure is represented as: ITO (130 nm)/compound 4-8 HT3 (2%) (20 nm)/compound 4-8(105nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Comparative example B
The device structure is represented as: ITO (130nm)/HAT-CN (20nm)/HT1(105nm)/HT2(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Compared with the comparative example B, the device of the device examples B1-B4 of the present invention has the same manufacturing process, and the same substrate and electrode material are adopted, and the film thickness of the electrode material is kept consistent, except that the hole injection material and the hole transport material in the device are replaced, and the hole injection layer is doped with HT-3 with the mass fraction of 2%, so that the injection and transport capability of the holes is improved at the same time.
The devices obtained from examples B1-B4 and comparative example B were at 10mA/cm2The performance tests were performed at current densities and the results are shown in table 5.
TABLE 5
As shown in the above table, the compounds used in examples B1-B4, which are used as the hole injection layer host material and the hole transport layer of the device, bring about excellent hole transport ability for the device, lower driving voltage, higher current efficiency and light emission efficiency, and exhibit better stability and lifetime, as compared to comparative example B.
To further verify the performance advantages of the present invention, an OLED device having the following structure was fabricated in the manner described above in example 1.
Example C1
The device structure is represented as: ITO (130nm)/HAT-CN (5nm)/HT1(110 nm)/compound 1-46(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example C2
The device structure is represented as: ITO (130nm)/HAT-CN (5nm)/HT1(110 nm)/compound 2-57(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example C3
The device structure is represented as: ITO (130nm)/HAT-CN (5nm)/HT1(110 nm)/compound 3-77(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Example C4
The device structure is represented as: ITO (130nm)/HAT-CN (5nm)/HT1(110 nm)/compound 4-80(20nm)/EB: BD (25nm)/ET: LiQ (25nm)/LiF (1nm)/Al (150 nm).
Compared with the comparative example A, the device manufacturing process of the device example C1-C4 of the invention is completely the same, and the same substrate and electrode material are adopted, and the film thickness of the electrode material is also kept consistent, except that the electron blocking layer HT2 in the device is replaced.
The devices obtained in examples C1-C4 and comparative example A were placed at 10mA/cm2The performance tests were performed at current densities and the results are shown in table 6.
TABLE 6
As shown in the above table, the compounds used in examples C1-C4, which were used as electron blocking layers of the devices, exhibited higher current efficiency and luminous efficiency, and exhibited better stability and lifetime, as compared to comparative example a.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. An organic compound having a symmetrical iso-substituted azaspirobifluorene structure, characterized by having a structure represented by formula (1):
in the formula (1), Z1、Z2、Z3、Z4Of which only one is a nitrogen atom and the remainder are CR1；
Ar1、Ar2、Ar3、Ar4Each independently represents a substituted or unsubstituted aryl or heterocyclic aryl group, and Ar1And Ar2Optionally by E1Are linked to each other to form a ring, Ar3And Ar4Optionally by E2Are connected with each other to form a ring; e1And E2Each independently represents a single bond, CR2R3、NR4-O-or-S-; ar (Ar)1(Ar2)N-(L1)m-and- (L)2)n-NAr3(Ar4) Different, the substitution positions of the two are symmetrical by taking the spiro carbon atom as the center;
L1and L2Each independently represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring-forming carbon atoms;
m and n each independently represent an integer of 0 to 3, and when m > 1, m L1Are the same or different from each other, when n > 1, n L2Are the same or different from each other;
R1、R2、R3、R4each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group.
2. The organic compound according to claim 1, wherein in the formula (1), Ar is1、Ar2、Ar3、Ar4Each independently represents a substituted or unsubstituted phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl or spirobifluorenyl group, or a substituted or unsubstituted dibenzothienyl, dibenzofuranyl or carbazolyl group.
3. The organic compound according to claim 1, wherein L in the formula (1)1And L2Are all single bonds; preferably, m, n each independently represent 0 or 1; preferably, in the formula (1), R1、R2、R3、R4Each independently represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, phenyl, 1-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, methoxy; more preferably, R1、R2、R3、R4Each independently represents hydrogen or phenyl.
4. The organic compound according to claim 1, wherein the formula (1) is represented by any one of the following formulae (2) to (5):
in the formulae (2) to (5), Z1、Z2、Z3、Z4、Ar1、Ar2、Ar3And Ar4Have the same definitions as above.
5. The organic compound according to claim 1, wherein the formula (1) is represented by any one of the following formulae (6) to (21):
and in the formulae (6) to (21), Ar1、Ar2、Ar3And Ar4Have the same definitions as above.
6. The organic compound of any one of claims 1 to 5, wherein Ar is Ar1、Ar2、Ar3And Ar4Each independently selected from the following structures:
wherein R is5、R6And R7Each independently is hydrogen, deuterium, a halogen group, a cyano group, a silyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted boron atom, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
7. The organic compound according to claim 1, wherein the organic compound is any one of the following compounds:
8. use of an organic compound having a symmetrically iso-substituted azaspirobifluorene structure according to any one of claims 1 to 7 in an OLED device.
9. An organic electroluminescent element comprising a cathode, an anode and one or more organic material layers disposed between the cathode and the anode, wherein at least one of the organic material layers comprises the organic compound according to any one of claims 1 to 7.
10. The organic electroluminescent element according to claim 9, wherein at least one of the organic material layers is a hole injection layer, and at least one of the hole injection layers contains the organic compound according to any one of claims 1 to 7.
11. The organic electroluminescent element according to claim 9, wherein the organic material layer is a plurality of layers, at least two of which are hole transport layers, and at least one of the hole transport layers comprises the organic compound according to any one of claims 1 to 7.
12. The organic electroluminescent element according to claim 9, wherein the organic material layer is a plurality of layers, at least one of which is a hole transport layer and at least one of which is a hole injection layer, and the organic compound according to any one of claims 1 to 7 is contained in each of the hole transport layer and the hole injection layer.
13. The organic electroluminescent element according to claim 9, wherein the organic material layer is a plurality of layers, at least one of which is an electron blocking layer, and the electron blocking layer contains the organic compound according to any one of claims 1 to 7.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720203A (en) * | 2014-12-19 | 2016-06-29 | 三星显示有限公司 | Organic light-emitting device |
| CN106831581A (en) * | 2017-02-10 | 2017-06-13 | 上海大学 | A kind of azepine spirobifluorene derivative and preparation method thereof |
| CN108997342A (en) * | 2018-08-20 | 2018-12-14 | 上海大学 | A kind of two fluorene compound of more azaspiros and the organic electro-optic device containing the compound |
| CN109776395A (en) * | 2019-03-20 | 2019-05-21 | 北京燕化集联光电技术有限公司 | A kind of cavitation material and the preparation method and application thereof that fluorine-containing spiral shell two is fluorene structured |
| CN109776396A (en) * | 2019-03-20 | 2019-05-21 | 北京燕化集联光电技术有限公司 | A kind of organic compound and the preparation method and application thereof fluorene structured with spiral shell two |
| CN109810083A (en) * | 2017-11-21 | 2019-05-28 | 上海自旭光电科技有限公司 | Compound for organic light emitting diodde desplay device |
| CN109942440A (en) * | 2019-04-25 | 2019-06-28 | 北京燕化集联光电技术有限公司 | A kind of OLED material and the preparation method and application thereof fluorene structured with spiral shell two |
| CN109970577A (en) * | 2019-04-25 | 2019-07-05 | 北京燕化集联光电技术有限公司 | It is a kind of with the compound and the preparation method and application thereof fluorene structured containing methylspiro two |
| CN110066222A (en) * | 2018-10-25 | 2019-07-30 | 常州强力电子新材料股份有限公司 | Containing the fluorene structured organic compound of spiral shell two and its application in OLED device |
-
2019
- 2019-09-20 CN CN201910894427.3A patent/CN112538047A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720203A (en) * | 2014-12-19 | 2016-06-29 | 三星显示有限公司 | Organic light-emitting device |
| CN106831581A (en) * | 2017-02-10 | 2017-06-13 | 上海大学 | A kind of azepine spirobifluorene derivative and preparation method thereof |
| CN109810083A (en) * | 2017-11-21 | 2019-05-28 | 上海自旭光电科技有限公司 | Compound for organic light emitting diodde desplay device |
| CN108997342A (en) * | 2018-08-20 | 2018-12-14 | 上海大学 | A kind of two fluorene compound of more azaspiros and the organic electro-optic device containing the compound |
| CN110066222A (en) * | 2018-10-25 | 2019-07-30 | 常州强力电子新材料股份有限公司 | Containing the fluorene structured organic compound of spiral shell two and its application in OLED device |
| CN109776395A (en) * | 2019-03-20 | 2019-05-21 | 北京燕化集联光电技术有限公司 | A kind of cavitation material and the preparation method and application thereof that fluorine-containing spiral shell two is fluorene structured |
| CN109776396A (en) * | 2019-03-20 | 2019-05-21 | 北京燕化集联光电技术有限公司 | A kind of organic compound and the preparation method and application thereof fluorene structured with spiral shell two |
| CN109942440A (en) * | 2019-04-25 | 2019-06-28 | 北京燕化集联光电技术有限公司 | A kind of OLED material and the preparation method and application thereof fluorene structured with spiral shell two |
| CN109970577A (en) * | 2019-04-25 | 2019-07-05 | 北京燕化集联光电技术有限公司 | It is a kind of with the compound and the preparation method and application thereof fluorene structured containing methylspiro two |
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